Herbicidal sulfonamides

ABSTRACT

This invention relates to benzylsulfonylureas which are active pre- and post-emergence herbicides.

RELATED APPLICATIONS

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 306,212, filed Sept. 29, 1981, which is in turn acontinuation-in-part of copending application U.S. Ser. No. 203,638,filed Nov. 3, 1980, both now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novel benzylsulfonylureas. The compounds ofthis invention and their agriculturally suitable salts, are useful asagricultural chemicals, e.g., herbicides.

Netherlands Patent No. 121,788, published Sept. 15, 1966, discloses thepreparation of compounds of the following Formula and their use asgeneral or selective herbicides: ##STR1## wherein

R₁ and R₂ may independently be alkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

U.S. Pat. No. 3,637,366 discloses compounds having the formula: ##STR2##wherein

R₁ is hydrogen or lower saturated aliphatic acyl; and

R₂ is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.The disclosed compounds are said to provide control of crabgrass, cress,endive, clover and Poa annua.

French Patent No. 1,468,747 discloses the following para-substitutedphenylsulfonamides as being useful as antidiabetic agents: ##STR3##wherein

R=H, halogen, CF₃ or alkyl.

Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR4## wherein

R is butyl, phenyl or ##STR5##

R₁ is hydrogen or methyl.

When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g),the compounds in which R is butyl and phenyl were most potent. Theothers were of low potency or inactive.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 591633 e] describes the synthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:##STR6## Based upon similarity to a known compound, the authorspeculated that the foregoing compound might have a hypoglycemicactivity.

Substituted-pyrimidinyl sulfonylureas of the following formula, whichare also para-substituted on the phenyl ring, are disclosed in FarmcoEd. Sco., 12, 586 (1957) [Chem. Ab., 53, 18052 g (1959)]: ##STR7##wherein

R=H or CH₃.

U.S. Pat. No. 4,127,405 teaches compounds which are useful forcontrolling weeds in wheat having the formula: ##STR8## wherein

R₁ is ##STR9##

R₃ and R₆ are independently hydrogen, fluorine, chlorine, bromine,iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro,trifluoromethyl, cyano, CH₃ S(O)_(n) -- or CH₃ CH₂ S(O)_(n) --;

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;

R₇ is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atomsor alkoxy of 1-2 carbon atom;

R₈ is hydrogen, methyl, chlorine or bromine;

R₉ and R₁₀ are independently hydrogen, methyl, chlorine or bromine;

W and Q are independently oxygen or sulfur;

n is 0, 1 or 2;

X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbonatoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Y is methyl or methoxy; or their agriculturally suitable salts; providedthat:

(a) when R₅ is other than hydrogen, at least one of R₃, R₄, R₆ and R₇ isother than hydrogen and at least two of R₃, R₄, R₆ and R₇ must behydrogen;

(b) when R₅ is hydrogen and all of R₃, R₄, R₆ and R₇ are other thanhydrogen, then all of R₃, R₄, R₆ and R₇ must be either chlorine ormethyl; and

(c) when R₃ and R₇ are both hydrogen, at least one of R₄, R₅ or R₆ mustbe hydrogen.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat, and the like. Thecurrent population explosion and concomitant world food and fibershortage demand improvements in the efficiency of producing these crops.Preventing or minimizing loss of a portion of such valuable crops bykilling, or inhibiting the growth of undesired vegetation is one way ofimproving this efficiency. A wide variety of materials useful forkilling or inhibiting (controlling) the growth of undesired vegetationis available; such materials are commonly referred to as herbicides. Theneed still exists however, for more effective herbicides.

SUMMARY OF THE INVENTION

This invention relates to compounds of Formula I and theiragriculturally suitable salts, suitable agricultural compositionscontaining them, and their method-of-use as general and selective pre-and/or post-emergence herbicides and as plant growth regulants.##STR10## wherein

R₁ is F, Cl, Br, CF₃, C₁ -C₃ alkoxy, C₁ -C₃ alkyl, NO₂, CO₂ R₄, SO₂ R₅,SO₂ NR₆ R₇, SO₂ N(OCH₃)CH₃, SO₂ OCH₂ CF₃, OSO₂ R₅ or CH₂ L;

L is SO₂ NR₆ R₇, OCH₃, OC₂ H₅, CO₂ CH₃ or CO₂ C₂ H₅ ;

R₂ is H, Cl, Br, F, CF₃ or OCH₃ ;

R₄ is C₁ -C₃ alkyl, CH₂ CH═CH₂, CH₂ CH₂ Cl, or CH₂ CH₂ OCH₃ ;

R₅ is C₁ -C₃ alkyl or CF₃ ;

R₆ and R₇ are independently C₁ -C₃ alkyl;

R₈ is H or CH₃ ;

R₉ is H or C₁ -C₃ alkyl;

R₃ is ##STR11##

W is O or S;

X is CH₃, OCH₃ or Cl;

Y is CH₃, C₂ H₅, OCH₃, OC₂ H₅, CH₂ OCH₃, NH₂, NHCH₃ or N(CH₃)₂ ;

Z is CH or N;

X₁ is H, Cl, CH₃, OCH₃ or OC₂ H₅ ;

X₂ is CH₃, C₂ H₅, OCH₃ or OC₂ H₅ ;

X₃ is CH₃ or OCH₃ ; and

Y₁ is CH₃ or OCH₃ ; and their agriculturally suitable salts; providedthat:

(1) when W is S, then R₈ is H;

(2) the total number of carbon atoms of R₆ and R₇ is less than or equalto 4; and

(3) when X is Cl, then Z is CH and Y is NH₂, NHCH₃, N(CH₃)₂ or OCH₃.

Preferred for their higher herbicidal activity and/or more favorableease of synthesis are:

(1) Compounds of Formula I wherein R₂ is H; R₈ is H; and W is O;

(2) Compounds of Preferred (1) wherein R₁ is CF₃, NO₂, C₁ -C₃ alkoxy,CO₂ R₄, SO₂ R₅, SO₂ NR₆ R₇, SO₂ N(OCH₃)CH₃ or OSO₂ R₅ ; R₉ is H; X₃ isOCH₃ ; and Y₁ is OCH₃ ;

(3) Compounds of Preferred (2) wherein R₄ is CH₃ or C₂ H₅ ; R₅ is CH₃ orCF₃ ; and R₆ and R₇ are independently CH₃ or C₂ H₅ ;

(4) Compounds of Preferred (3) wherein ##STR12##

(5) Compounds of Preferred (4) wherein R₁ is CF₃, NO₂, CO₂ CH₃, SO₂ CH₃,SO₂ N(CH₃)₂, SO₂ N(OCH₃)CH₃ or OSO₂ CH₃ ; and

(6) Compounds of Preferred (5) wherein X and Y are independently CH₃ orOCH₃.

Specifically preferred are:

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p. 207°-208°;

N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p. 185°-188°;

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p. 194°-195°;

N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p. 165°-168°;

N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p. 192°-194°;

2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 179°-183°;

2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 154°-156°;

2-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 162°-165°;

2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 135°-140°;

2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 165°-167°;

2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester, m.p. 125°-130°; and

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide,m.p. 202°-204° (d).

This invention also relates to compounds of Formula II which are usefulintermediates for the preparation of the herbicidal compounds of FormulaI: ##STR13## wherein

R₁ is F, Cl, Br, CF₃, C₁ -C₃ alkoxy, C₁ -C₃ alkyl, NO₂, CO₂ R₄, SO₂ R₅,SO₂ NR₆ R₇, SO₂ N(OCH₃)CH₃, SO₂ OCH₂ CF₃, OSO₂ R₅ or CH₂ L;

L is SO₂ NR₆ R₇, OCH₃, OC₂ H₅ ; CO₂ CH₃ or CO₂ C₂ H₅ ;

R₂ is H, Cl, Br, F, CF₃ or OCH₃ ;

R₄ is C₁ -C₃ alkyl, CH₂ CH═CH₂, CH₂ CH₂ Cl, or CH₂ CH₂ OCH₃ ;

R₅ is C₁ -C₃ alkyl or CF₃ ;

R₆ and R₇ are independently C₁ -C₃ alkyl; and

R₉ is H or C₁ -C₃ alkyl; provided that the total number of carbon atomsof R₆ and R₇ is less than or equal to 4.

Preferred intermediates for their more favorable ease of synthesisand/or the higher herbicidal activity of the derived products are:

(1) Compounds of Formula II wherein R₂ is H;

(2) Compounds of Preferred (1) wherein R₁ is CF₃, NO₂, C₁ -C₃ alkoxy,CO₂ R₄, SO₂ R₅, SO₂ NR₆ R₇, SO₂ N(OCH₃)CH₃ or OSO₂ R₅ ; and

(3) Compounds of Preferred (2) wherein R₄ is CH₃ or C₂ H₅ ; R₅ is CH₃ orCF₃ ; and R₆ and R₇ are independently CH₃ or C₂ H₅.

Especially preferred as a selective herbicide for rice are compounds ofthe following formula: ##STR14## wherein

R₁ is Cl, NO₂, CO₂ CH₃, SO₂ CH₃ OSO₂ CH₃ or SO₂ N(CH₃)₂

Synthesis

The compounds of Formula I, where W=O, may be prepared as shown below inEquation 1 by the reaction of an appropriate benzenemethanesulfonylisocyanate, II with an appropriate aminoheterocycle, III. ##STR15##wherein

R₁, R₂, R₃, R₈ and R₉ are as previously defined.

The reaction of Equation 1 is best carried out in an inert aproticsolvent such as methylene chloride, tetrahydrofuran or acetonitrile at atemperature between 20° and 80°. A catalytic amount of1,4-diazabicyclo[2,2,2]octane (DABCO) may be used to accelerate thereaction. In cases in which the products are insoluble in the reactionsolvent, they may be isolated by simple filtration. When the productsare soluble, they may be isolated by evaporation of the solvent andtrituration of the residue with solvents such as 1-chlorobutane, diethylether or methanol and filtration.

Compounds of Formula I in which W=S and R₈ =H may be prepared by thereaction shown in Equation 2. ##STR16## wherein

R₁, R₂, R₃, and R₉ are as previously defined.

The reaction of Equation 2 is best carried out by suspending thesulfonamide, the isothiocyanate and an equivalent of a base such asanhydrous potassium carbonate in a solvent such as acetone, methyl ethylketone, acetonitrile or ethyl acetate. The reaction is stirred at25°-80° for 1 to 24 hours. In some cases, the product precipitates fromthe reaction mixture and can be filtered off, suspended in dilutemineral acid, filtered again and washed with cold water. If the productdoes not precipitate, it can be isolated by evaporation of the solvent,trituration of the residue with dilute mineral acid and filtration ofthe insoluble product.

The heterocyclic isothiocyanates, V, which are used in the procedure ofEquation 2 are prepared according to the method of Japan PatentApplication Pub. Kokai 51-143686, June 5, 1976; or that of W. Abrahamand G. Barnikow, Tetrahedron 29, G91-7 (1973) both of which are hereinincorporated by reference.

The benzenemethanesulfonyl isocyanates of Formula II may be prepared asshown in Equation 3, by phosgenation of the sulfonamides of Formula IVin the presence of butyl isocyanate. The sulfonyl isocyanates of FormulaII may also be prepared, as shown in Equation 4, by phosgenation of thebutyl ureas of Formula VI. ##STR17## wherein

R₁, R₂ and R₉ are as previously defined.

The above reaction is carried out by heating a mixture of theappropriate sulfonamide (IV), an alkyl isocyanate such as butylisocyanate and a catalytic amount of a tertiary amine such as1,4-diazabicyclo[2,2,2]octane (DABCO) in xylene, or other inert solventof boiling point ≧135°, to approximately 135°. Phosgene is then added tothe mixture over a 1-6 hour period at 125°-135° until an excess ofphosgene is present as indicated by a permanent drop in the boilingpoint to less than 130°. The mixture is cooled and filtered to remove asmall amount of insoluble by-products. The solvent and the alkylisocyanate are distilled off in vacuo leaving a residue of the crude,sulfonyl isocyanate, II, which can be used without further purification.##STR18## wherein

R₁, R₂ and R₉ are as previously defined.

The compounds of Formula VI are conveniently prepared by stirring amixture of the sulfonamides, IV, anhydrous potassium carbonate, andn-butyl isocyanate in acetone or methyl ethyl ketone at 25°-80° untilall of the isocyanate has reacted. The products are isolated byquenching in dilute mineral acid and recrystallizing the solid product.The compounds VI are treated with phosgene and a catalytic amount ofDABCO in refluxing xylene or chlorobenzene in a manner analogous to thatdescribed in Equation 3. Ihe sulfonamides of Formula IV can be preparedfrom the appropriately substituted benzyl chlorides or benzyl bromidesVII by the sequence of reactions described in Equation 5 below.##STR19## wherein

A is chlorine or bromine; and R₁, R₂ and R₉ are as previously defined.

Equation (5a)

In Equation (5a) a benzyl halide of Formula VII is reacted with thioureain protic solvents such as methanol or ethanol, or aprotic solvents suchas methylene chloride or benzene. Temperatures of 40°-80° over one-halfto 4 hours are typically required to complete the reaction. The productsalts, VIII, are isolated by cooling and filtration or by concentrationto remove the solvent. The salts, VIII, are generally sufficiently pureto be carried on directly to step (5b) without further purification.

Equation (5b)

In Equation (5b), the hydrochloride salts VIII (A=chlorine) aresuspended in water and contacted with at least three equivalents ofchlorine at between 5° and 20°. When the corresponding hydrobromidesalts VIII (A=bromine) are used, it is generally advantageous toexchange the bromide ion for the nitrate ion before chlorination bytreatment with an aqueous solution of one equivalent of silver nitrate;the precipitated silver bromide is removed by filtration and thefiltrate treated as described above. The product sulfonyl chlorides ofFormula IX are isolated by filtration and washing with water. No furtherpurification of the sulfonyl chlorides IX is necessary.

Equation (5c)

In Equation (5c), the sulfonyl chlorides of Formula IX are suspended inan aprotic solvent such as diethyl ether, 1-chlorobutane, methylenechloride, or tetrahydrofuran and contacted with an excess of anhydrousammonia at a temperature of 0° to 25°. The product sulfonamides ofFormula IV are isolated by filtration and washing with water to removethe by-product ammonium chloride and concentrating the organic solution.Frequently, the crude sulfonamides may be used directly to prepare thesulfonyl isocyanates of Formula II. However, they may also be purifiedfirst by recrystallization from a suitable organic solvent such asethanol, acetonitrile or chloroform.

The synthesis of heterocyclic amine derivatives such as those depictedby Formula III has been reviewed in "The Chemistry of HeterocyclicCompounds", a series published by Interscience Publ., New York andLondon. Aminopyrimidines are described by D. J. Brown in "ThePyrimidines", Vol. XVI of the above series.

The synthesis of the bicyclic pyrimidines of Formula III is described inthe following references:

Braker, Sheehan, Spitzmiller and Lott, J. Am. Chem. Soc., 69, 3072(1947);

Mitter and Bhattacharya, Quart. J. Indian. Chem. Soc., 4, 152 (1927);

Shrage and Hitchings, J. Org. Chem., 16, 1153 (1951);

E. Bisayni et al., Bull. Soc. Chem. Fr., 803 (1969);

Caldwell, Kornfeld and Donnell, J. Am. Chem. Soc., 63, 2188 (1941); and

Fissekis, Myles and Brown, J. Org. Chem., 29, 2670 (1964). All of theabove are herein incorporated by reference.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by treating compounds of Formula I witha solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g. hydroxide, alkoxide, carbonate orhydride) quaternary amine salts can be made by similar techniques.Detailed examples of such techniques are given in U.S. Pat. No.4,127,405, the disclosure of which is herein incorporated by reference.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centigrade and all parts are by weight unless otherwiseindicated.

EXAMPLE 1 2-Nitrophenylmethyl carbamimidothioate hydrochloride

A solution of 153.9 g of o-nitrobenzylchloride and 68.5 g of thiourea in900 ml of #2B ethanol was stirred at reflux temperature (80°) for 11/4hours. The solution was cooled to 60° and 1.1 liters of 1-chlorobutanewas added. Further cooling to 15° produced a heavy precipitate. Theprecipitate was filtered, washed with 1-chlorobutane and dried to yield185.9 g of 2-nitrophenylmethyl carbamimidothioate hydrochloride, m.p.190°-192°.

NMR (DMSO-d₆)δ: 4.85 (s, 1.84, --CH₂ --); 7.4-8.4 (m, 4.2H, 4aromatics); 9.7 (broad singlet, 4.0H, 4 NH's).

EXAMPLE 2 2-Nitrophenylmethanesulfonyl chloride

To a suspension of 34.7 g of the product of Example 1 in 300 ml of waterwas added 24.0 ml of liquid chlorine at 10°-15° over a 45 minute period.After stirring an additional 30 minutes at 10°-12° the product wasfiltered off, washed with water and air dried in a fume hood overnightto give 31.6 g of 2-nitrophenylmethanesulfonyl chloride, m.p.62.5°-64.0°.

EXAMPLE 3 2-Nitrophenylmethanesulfonamide

To a suspension of 29.4 g of the product of Example 2 in 250 ml ofdiethyl ether was added 6.5 ml of anhydrous ammonia at 5°-15°. Afterstirring at 15°-25° for 1 hour, the product was filtered off, washedwith ether, and water and oven dried at 60° to give 20.5 g of2-nitrophenylmethanesulfonamide, m.p.=134°-136°.

NMR (DMSO-d₆)δ: 4.7 (s, 1.8H, --CH₂ --); 6.8-7.3 (broad singlet, 1.8H,--SO₂ NH₂); 7.5-8.3 (m, 4.4H, 4 aromatics).

EXAMPLE 4 2-Nitrophenylmethanesulfonyl isocyanate

A solution of 9.0 g of the product of Example 3, 4.2 g of butylisocyanate and 0.1 g of DABCO in 80 ml of dry xylenes was heated to136°. To this solution was added 3.0 ml of liquid phosgene at such arate as to maintain the temperature between 125° and 136°. This additionrequired about 21/2 hours. The solution was cooled to 25°, filteredunder nitrogen and stripped in vacuo to give crude2-nitrophenylmethanesulfonyl isocyanate as a viscous, moisture-sensitiveoil showing a sulfonyl isocyanate peak in the infrared at 2230 cm⁻¹.

EXAMPLE 5N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide

Under a nitrogen atmosphere, a mixture of 2.2 g of the product ofExample 4, 0.9 g of 4,6-dimethoxy-2-aminopyrimidine and a few crystalsof DABCO in 15 ml of dry acetonitrile was heated at 50°-55° for 1 hour,followed by stirring at room temperature overnight. The product wasfiltered, washed first with acetonitrile then 1-chlorobutene and ovendried in vacuo at 60° to give 1.8 g ofN-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide,m.p.=207°-208°(d).

NMR (DMSO-d₆)δ: 3.8 (s, 6.1H, Het-OCH₃ 's); 5.3 (s, 1.8H, --CH₂ --); 6.0(s, 1.0H, Het-H); 7.7-8.3 (m, 4.1H, 4 aromatics); 10.9 (s, 1.0H, NH);˜12.5 (broad singlet, 0.9H, NH).

Anal. Calcd. for C₁₄ H₁₅ N₅ O₇ S: C, 42.31; H, 3.80; N, 17.63. Found: C,42.6, 42.6; H, 3.9, 3.9; and N, 17.7, 17.8.

EXAMPLE 6 2-(Methylsulfonyl)phenylmethyl carbamimidothioate hydrobromide

A solution of 36.5 g of 2-(methylsulfonyl)benzyl bromide and 11.4 g ofthiourea in 500 ml absolute ethanol was stirred at reflux temperaturefor 11/2 hours and then allowed to cool to room temperature. Uponstanding, the solution yielded white feather-like crystals which werecollected by filtration, washed with cold 1-chlorobutane, and dried invacuo. The yield of 2-(methylsulfonyl)phenylmethyl carbamimidothioatehydrobromide, m.p. 203°-206° C., was 36.3 g.

NMR (DMSO-d₆)δ: 3.3 (s, 3H, --CH₃); 4.9 (s, 2H, --CH₂ --); 7.6-8.1 (m,4H, aromatics); 9.4 (broad singlet, 4H, NH's).

EXAMPLE 7 2-(Methylsulfonyl)phenylmethanesulfonyl chloride

A solution of 29.5 g of the product from Example 6 in 450 ml water wasreacted with 15.5 g of silver nitrate in 45 ml water. The resultingprecipitate of silver bromide was removed by filtration and washed with50 ml water. The aqueous filtrate was then diluted with 180 ml ofglacial acetic acid and reacted with 15 ml of liquid chlorine at 0°-5°C., added over a period of 30 minutes. The reaction mixture was stirredfor an additional 13/4 hours while the temperature was allowed to riseto 25° C. The light yellow solid was collected by filtration, washedwith water and air-dried in a fume hood overnight to yield 22 g of2-(methylsulfonyl)phenylmethanesulfonyl chloride which was used withoutfurther purification.

NMR (DMSO-d₆)δ: 3.4 (s, 3H, --CH₃); 4.4 (s, 2H, --CH₂ --); 7.5-7.9 (m,4H, aromatics).

EXAMPLE 8 2-(Methylsulfonyl)phenylmethanesulfonamide

To a suspension of 22 g of the product from Example 7 in 500 ml drydiethyl ether was added 25 ml anhydrous ammonia at 0°-5° C. The reactionmixture was stirred at 5°-15° C. for 45 minutes and then allowed to warmto room temperature over a one hour period. The solvent was removed invacuo and the resulting solids were washed with water and ether. Furtherevaporation of the solvent in vacuo afforded 4.6 g of(2-methylsulfonyl)phenylmethanesulfonamide, m.p. 124°-127° C., as a tansolid.

NMR (DMSO-d₆)δ: 3.3 (s, 3H, --CH₃); 5.0 (s, 2H, --CH₂ --); 7.6-7.8 (m,3H, aromatics); 8.0 (m, 1H, aromatic).

IR(KBr): 3320, 3260, 1340, 1300, 1150 cm⁻¹.

EXAMPLE 9N-[(n-butyl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide

A mixture of 5.0 g of the product from Example 8, 4.2 g of anhydrouspotassium carbonate, and 3.4 ml of n-butyl isocyanate in 60 ml methylethyl ketone was heated to reflux temperature for 5 hours. After coolingto room temperature, the solution was poured into 200 ml ice-water. Thisaqueous solution was acidified to ca. pH 1 by the slow addition ofconcentrated hydrochloric acid resulting in a white precipitate. Thesolids were filtered, washed with water, 1-chlorobutane, and then driedin a vacuum desiccator to give 6.2 g ofN-[(n-butyl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide asa tan solid, m.p. 149°-151° C. (dec.).

NMR (DMSO-d₆)δ: 0.9-1.6 (m, 7H, --CH₂ CH₂ CH₃); 3.0-3.2 (m, 2H, --CH₂--); 3.4 (s, 3H, --CH₃); 5.4 (s, 2H, --CH₂ --); 6.6 (br s, 1H, N--H);7.6-7.9 (m, 3H, aromatics); 8.0-8.2 (m, 1H, aromatic).

IR(KBr): 3350, 3250, 1700, 1320, 1150 cm⁻¹.

EXAMPLE 10 2-(Methylsulfonyl)phenylmethanesulfonyl isocyanate

A suspension of 5.5 g of the product from Example 9 and 0.1 g of1,4-diazabicyclo[2.2.2]octane (DABCO) in 100 ml dry xylenes was heatedto 125°-130° C. under an atmosphere of nitrogen. At this temperature,2.5 ml of phosgene was added dropwise at a rate that maintained thetemperature above 120° C. After completion of the addition (ca. onehour), the solution was heated at 125° C. for another two hours. Aftercooling to room temperature, the mixture was filtered under nitrogen andconcentrated in vacuo to afford crude2-(methylsulfonyl)phenylmethanesulfonyl isocyanate as a yellow semisolidwhich was carried on to the next step without purification. The IRspectrum of this intermediate displayed a characteristic isocyanateabsorption at 2240 cm⁻¹.

EXAMPLE 11N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide

To a solution of 3.0 g of the product from Example 10 in 30 ml drydichloromethane was added 1.2 g of 4,6-dimethoxy-2-aminopyrimidine andthe yellow homogeneous solution was stirred at room temperatureovernight. The desired product, which had precipitated, was collected byfiltration, washed with 1-chlorobutane, and dried in vacuo. The yield ofN-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide,m.p. 180°-182° C., was 2.4 g of white solid.

NMR (DMSO-d₆)δ: 3.8 (s, 6H, heterocyclic OCH₃ 's); 5.4 (s, 2H, --CH₂--); 6.0 (s, 1H, heterocyclic H); 7.6-8.0 (m, 4H, aromatics); 10.6 (brs, 1H, N--H).

IR(KBr): 1730, 1610, 1580, 1370, 1350, 1150 cm⁻¹.

EXAMPLE 12 1-(2-Nitrophenyl)ethyl carbamimidothioate hydrobromide

A solution of 33.5 g of 1-(2-nitrophenyl)ethyl bromide and 11.4 g ofthiourea in 375 ml absolute ethanol was stirred at reflux temperaturefor 31/2 hours. The reaction mixture was allowed to cool to roomtemperature and was concentrated to one-half volume in vacuo. Thesolution was then cooled to ca. -60° C. and 1-chlorobutane was addeduntil a gummy solid formed. The supernatant was decanted and the residuedried in vacuo to give 38 g of 1-(2-nitrophenyl)ethyl carbamimidothioatehydrobromide as a light orange solid which was not further purified.

NMR (DMSO-d₆)δ: 3.7 (br d, J=7 Hz, 3H, --CH₃); 5.5 (br q, J=7 Hz, 1H,--CH<); 7.5-8.0 (m, 4H, aromatics); 9.4 (br s, 4H, N--H's).

EXAMPLE 13 1-(2-Nitrophenyl)ethanesulfonyl chloride

A solution of 37.6 g of the product from Example 12 in 700 ml water wasreacted with 21.9 g of silver nitrate in 60 ml water. The resultingprecipitate of silver bromide was removed by filtration and washed withwater. Glacial acetic acid (250 ml) was added to the aqueous filtrateand this solution was cooled to 0° C. and treated with 23 ml of liquidchlorine, added over a period of about 45 minutes. After being stirredfor one hour at 0°-5° C., the reaction mixture was allowed to warm toroom temperature over an additional one hour period. The solids whichhad formed were filtered and washed with water. Air-drying overnight ina fume hood gave 27.5 g of 1-(2-nitrophenyl)ethanesulfonyl chloride as alight yellow solid.

NMR (DMSO-d₆)δ: 2.1 (d, J=7 Hz, 3H, --CH₃); 6.2 (q, J=7 Hz, 1H, CH);7.6-8.1 (m, 4H, aromatics);

IR(KBr): 1530, 1350, 1160 cm⁻¹.

EXAMPLE 14 1-(2-Nitrophenyl)ethanesulfonamide

Liquid anhydrous ammonia (10 ml) was added to a stirred suspension ofthe product from Example 13 in 350 ml dry diethyl ether at 0°-5° C. overa period of 20 minutes. The reaction mixture was stirred at 0°-5° C. for30 minutes and was allowed to warm to room temperature over a two hourperiod. The solids were filtered and washed with diethyl ether.Concentration of the filtrate in vacuo gave a yellow solid which waswashed with water, 1-chlorobutane, and then dried under vacuum to yield17 g of 1-(2-nitrophenyl)ethanesulfonamide as a pale yellow solid, m.p.107°-109° C.

NMR (DMSO-d₆)δ: 1.7 (d, J=7 Hz, 3H, --CH₃); 5.0 (q, J=7 Hz, 1H, CH); 7.0(br s, 2H, NH₂); 7.4-8.0 (m, 4H, aromatics).

IR(KBr): 3340, 3260, 1350, 1310, 1160 cm⁻¹.

EXAMPLE 15 1-(2-Nitrophenyl)ethanesulfonyl isocyanate

A mixture of 16 g of the product from Example 14, 8.0 ml of n-butylisocyanate, and 0.2 g of 1,4-diazabicyclo[2.2.2]octane (DABCO) in 125 mldry xylenes was heated to 130°-135° C. for 11/2 hours. To this solutionwas added 6 ml of phosgene at a rate which maintained the temperatureabove 130° C. After completion of the addition (ca. one hour), thesolution was cooled and filtered under nitrogen. The filtrate wasconcentrated in vacuo to give the crude 1-(2-nitrophenyl)ethanesulfonylisocyanate as a viscous orange oil. The IR spectrum of this compounddisplayed a characteristic isocyanate absorption at 2240 cm⁻¹.

EXAMPLE 16N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)ethanesulfonamide

A solution of 4.0 g of the product from Example 15 and 2.2 g of4,6-dimethoxy-2-aminopyrimidine in 29 ml dry acetonitrile was heated toca. 60° C. for 11/2 hours and then stirred at room temperatureovernight. The product, which had precipitated, was collected and washedwith 1-chlorobutane and then dried in vacuo. The yield ofN-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)ethanesulfonamidewas 3.1 g white solid, m.p. 168°-170° C. NMR (DMSO-d₆)δ: 1.8 (d, J=7 Hz,3H, --CH₃); 3.8 (s, 6H, heterocyclic OCH₃ 's); 5.6 (q, J=7 Hz, 1H, CH);5.8 (s, 1H, heterocyclic H); 7.6-8.0 (m, 4H, aromatics); 10.6 (br s, 1H,N--H).

IR(KBr): 1720, 1610, 1580, 1360, 1200, 1150 cm⁻¹.

Using the procedures and examples described above and choosing theappropriate aminoheterocyclic and sulfonyl isocyanate, the compoundsdescribed in Tables 1-8 may be prepared.

The sulfonylisocyanate intermediates described in Table 9 may also beprepared using the procedures and examples described above.

                                      TABLE 1                                     __________________________________________________________________________     ##STR20##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X   Y      m.p. (°C.)                        __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           207-208° (d)                      NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             194-195° (d)                      NO.sub.2   H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             192-194° (d)                      Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           209-211° (d)                      Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             184-185° (d)                      Cl         H    O H  H    CH.sub.3                                                                          CH.sub. 3                                                                            202-204° (d)                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           179-183°                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                                                           162-165°                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             165-167°                          CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           214-216° (d)                      CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                                                           173-175° (d)                      CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             192-193.5° (d)                    F          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Br         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 O H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR21## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3 O                                                                        OCH.sub.3                                                                            179-181°                          CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CF.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR22## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             142-145°                          SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           167-170°                           ##STR23## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR24## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             169-171° (d)                      n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   3-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 CH.sub.2 O                             CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 CH.sub.2 O                             CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 OCH.sub.2                              CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 OCH.sub.2                              CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           202-204° (d)                      CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             172-178° (d)                      CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           180-182°                          NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3 O                                                                           168-170°                          NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                                                             119-121°                          NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                             140-144°                          NO.sub.2   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub. 7                                                                 CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    Cl  CH.sub.3 O                                      Cl         H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3 O                                      Cl         H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    Cl  NH.sub.2                                        Cl         H    O H  H    Cl  NHCH.sub.3                                      CH.sub.3   H    O H  H    Cl  N(CH.sub.3).sub.2                               CH.sub.3   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3 O                                      i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.2 CH.sub.3                               OCH.sub.2 CH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR25## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR26## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 OEt                                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        OCH.sub.3  H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        NH.sub.2                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        NHCH.sub.3                                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        N(CH.sub.3).sub.2                               CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          NH.sub.2                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          NHCH.sub.3                                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          N(CH.sub.3).sub.2                               CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.2 CH.sub.3                               __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR27##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X   Y      m.p. (°C.)                        __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           185-188° (d)                      NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             165-168° (d)                      NO.sub.2   H    O H  H    CH.sub.3                                                                          CH.sub.3                                        Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           198-199° (d)                      Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             193-195° (d)                      Cl         H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             212-214° (d)                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           154-156°                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                                                           135-140°                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             125-130°                          CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           185-189° (d)                      CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                                                           177-179° (d)                      CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             197.5-199° (d)                    F          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Br         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 O H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR28## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             181-184°                          n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             170-172°                          CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CF.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR29## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3                                                                          CH.sub.3 O                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR30## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR31## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                                                             176-179° (d)                      n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CF.sub. 3 SO.sub.2 O                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   3-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 CH.sub.2 O                             CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 CH.sub.2 O                             CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3 OCH.sub.2                              CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 OCH.sub.2                              CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                                                           187-192° (d)                      CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                                                          CH.sub.3                                                                             155-161° (d)                      NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3 O                                                                           166-169°                          NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                                                             147-149°                          NO.sub.2   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          NH.sub.2                                        CO.sub.2 CH.sub. 3                                                                       H    O H  H    CH.sub.3 O                                                                        NHCH.sub.3                                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          N(CH.sub.3).sub.2                               CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.2 CH.sub.3                               CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.2 CH.sub.3                               Cl         H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    CH.sub.3 O                                                                        NH.sub.2                                        Cl         H    O H  H    CH.sub.3                                                                          NHCH.sub.3                                      Cl         H    O H  H    CH.sub.3 O                                                                        N(CH.sub.3).sub.2                               Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.2 CH.sub.3                               CH.sub.3   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        OEt        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR32## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                         ##STR33## H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        OCH.sub.3  H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR34##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.1                                                                             m.p. (°C.)                             __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    CH.sub.3 O                                          Cl         H    O H  H    CH.sub.3                                            Cl         H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                          CH.sub.3   H    O H  H    CH.sub.3                                            F          H    O H  H    CH.sub.3                                            Br         H    O H  H    CH.sub.3                                             ##STR35## H    O H  H    CH.sub.3                                            CH.sub.3   H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            CF.sub.3   H    O H  H    CH.sub.3                                             ##STR36## H    O H  H    CH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3                                             ##STR37## H    O H  H    CH.sub.3                                             ##STR38## H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            NO.sub.2   3-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Cl O H  H    CH.sub.3                                            NO.sub.2   6-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Br O H  H    CH.sub.3                                            NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3                                            NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    H                                                   CO.sub.2 CH.sub.3                                                                        H    O H  H    H                                                   Cl         H    O H  H    H                                                   SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    H                                                   NO.sub.2   H    O H  H    OCH.sub.2 CH.sub.3                                  NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3                                            NO.sub.2   H    S H  H    H                                                   CO.sub.2 CH.sub. 3                                                                       H    O H  CH.sub.3                                                                           CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  H                                                   CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    OCH.sub.2 CH.sub.3                                  CO.sub.2 CH.sub.3                                                                        H    O H  H    Cl                                                  Cl         H    S H  H    H                                                   Cl         H    O CH.sub.3                                                                         H    CH.sub.3 O                                          Cl         H    O H  H    Cl                                                  Cl         H    O H  H    OCH.sub.2 CH.sub.3                                  CH.sub.3   H    S H  H    H                                                   CH.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3                                            SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3                                            OEt        H    O H  H    CH.sub.3                                             ##STR39## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3                                             ##STR40## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3                                            OCH.sub.3  H    O H  H    CH.sub.3                                            __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR41##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.1                                                                             m.p. (°C.)                             __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    CH.sub.3 O                                          Cl         H    O H  H    CH.sub.3                                            Cl         H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                          CH.sub.3   H    O H  H    CH.sub.3                                            F          H    O H  H    CH.sub.3                                            Br         H    O H  H    CH.sub.3                                             ##STR42## H    O H  H    CH.sub.3                                            CH.sub.3   H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            CF.sub.3   H    O H  H    CH.sub.3                                             ##STR43## H    O H  H    CH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3                                             ##STR44## H    O H  H    CH.sub.3                                             ##STR45## H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            NO.sub.2   3-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Cl O H  H    CH.sub.3                                            NO.sub.2   6-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Br O H  H    CH.sub.3                                            NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3                                            NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    H                                                   CO.sub.2 CH.sub.3                                                                        H    O H  H    H                                                   Cl         H    O H  H    H                                                   SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    H                                                   NO.sub.2   H    O H  H    OCH.sub.2 CH.sub.3                                  NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3                                            NO.sub.2   H    S H  H    H                                                   CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.3                                                                           CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  H                                                   CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    OCH.sub.2 CH.sub.3                                  CO.sub.2 CH.sub.3                                                                        H    O H  H    Cl                                                  Cl         H    S H  H    H                                                   Cl         H    O CH.sub.3                                                                         H    CH.sub.3 O                                          Cl         H    O H  H    Cl                                                  Cl         H    O H  H    OCH.sub.2 CH.sub.3                                  CH.sub.3   H    S H  H    H                                                   CH.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3                                            SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3                                            OEt        H    O H  H    CH.sub.3                                             ##STR46## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3                                             ##STR47## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3                                            OCH.sub.3  H    O H  H    CH.sub.3                                            __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________     ##STR48##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.1                                                                             m.p. (°C.)                             __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    CH.sub.3 O                                          NO.sub.2   H    O H  H    OCH.sub.2 CH.sub.3                                  NO.sub.2   H    O H  H    Cl                                                  NO.sub.2   H    O CH.sub.3                                                                         H    H                                                   NO.sub.2   H    S H  H    CH.sub.3                                            NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  H    OCH.sub. 2 CH.sub.3                                 CO.sub.2 CH.sub.3                                                                        H    O H  H    Cl                                                  CO.sub.2 CH.sub.3                                                                        H    O H  H    H                                                   CO.sub.2 CH.sub.3                                                                        H    S H  H    H                                                   CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    H                                                   Cl         H    O H  H    CH.sub.3                                            Cl         H    O H  H    CH.sub.3 O                                          Cl         H    O H  H    OCH.sub.2 CH.sub.3                                  Cl         H    O H  H    Cl                                                  Cl         H    O H  H    H                                                   Cl         H    S H  H    H                                                   Cl         H    O CH.sub.3                                                                         H    CH.sub.3                                            CH.sub.3   H    O H  H    CH.sub.3                                            CH.sub.3   H    O H  H    CH.sub.3 O                                          CH.sub.3   H    O H  H    OCH.sub.2 CH.sub.3                                  CH.sub.2 CH.sub.3                                                                        H    O H  H    Cl                                                  CH.sub.2 CH.sub.3                                                                        H    S H  H    H                                                   i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3                                            SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3                                            OEt        H    O H  H    CH.sub.3                                             ##STR49## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3                                             ##STR50## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3                                            OCH.sub.3  H    O H  H    CH.sub.3                                            F          H    O H  H    CH.sub.3                                            Br         H    O H  H    CH.sub.3                                             ##STR51## H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            CF.sub.3   H    O H  H    CH.sub.3                                             ##STR52## H    O H  H    CH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3                                             ##STR53## H    O H  H    CH.sub.3                                             ##STR54## H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            NO.sub.2   3-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Cl O H  H    CH.sub.3                                            NO.sub.2   6-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Br O H  H    CH.sub.3                                            NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3                                            NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________     ##STR55##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.2                                                                             m.p. (°C.)                             __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    CH.sub.3 CH.sub.2                                   Cl         H    O H  H    CH.sub.3                                            Cl         H    O H  H    CH.sub.3 CH.sub.2                                   CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 CH.sub.2                                   CH.sub.3   H    O H  H    CH.sub.3                                            F          H    O H  H    CH.sub.3                                            Br         H    O H  H    CH.sub.3                                             ##STR56##                                                                    CH.sub.3   H    O H  H    CH.sub.3 CH.sub.2                                   CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3                                            CF.sub.3   H    O H  H    CH.sub.3                                             ##STR57## H    O H  H    CH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3                                             ##STR58## H    O H  H    CH.sub.3                                             ##STR59## H    O H  H    CH.sub.3                                            CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3                                            CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3                                            NO.sub.2   3-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Cl O H  H    CH.sub.3                                            NO.sub.2   6-Cl O H  H    CH.sub.3                                            NO.sub.2   5-Br O H  H    CH.sub.3                                            NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3                                            NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-CF.sub.3                                                                         O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3                                            NO.sub.2   H    O H  H    CH.sub.3 O                                          NO.sub.2   H    O H  H    OCH.sub.2 CH.sub.3                                  NO.sub.2   H    S H  H    CH.sub.3                                            NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.2 CH.sub.3                                   CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    S H  H    CH.sub.3                                            CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                          CO.sub.2 CH.sub.3                                                                        H    O H  H    OCH.sub.2 CH.sub.3                                  Cl         H    O H  H    CH.sub.3 O                                          Cl         H    O H  H    OCH.sub.2 CH.sub.3                                  Cl         H    O CH.sub.3                                                                         H    CH.sub.3                                            Cl         H    O H  CH.sub.3                                                                           CH.sub.3                                            CH.sub.3   H    S H  H    CH.sub.3                                            CH.sub.3   H    O H  H    CH.sub.3 O                                          CH.sub.2 CH.sub.3                                                                        H    O H  H    OCH.sub.2 CH.sub.3                                  i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3                                            SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3                                            OCH.sub.2 CH.sub.3                                                             ##STR60## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3                                             ##STR61## H    O H  H    CH.sub.3                                            CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3                                            CH.sub. 2 OCH.sub.3                                                                      H    O H  H    CH.sub.3                                            CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3                                            CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3                                            OCH.sub.3  H    O H  H    CH.sub.3                                            __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR62##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.3                                                                           Y.sub.1                                                                           m.p. (°C.)                           __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O H  H    CH.sub.3                                                                          CH.sub.3                                        NO.sub.2   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    CH.sub.3                                                                          CH.sub.3                                        Cl         H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CH.sub.3   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                        F          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Br         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 O H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR63## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR64## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR65## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR66## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   3-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        5-CF.sub. 3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      OCH.sub.2 CH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR67## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR68## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR69##                                                                    R.sub.1    R.sub.2                                                                            W R.sub.8                                                                          R.sub.9                                                                            X.sub.3                                                                           Y.sub.1                                                                           m.p. (°C.)                           __________________________________________________________________________    NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O H  H    CH.sub.3                                                                          CH.sub.3                                        NO.sub.2   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        NO.sub.2   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub. 3 O                                     Cl         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O H  H    CH.sub.3                                                                          CH.sub.3                                        Cl         H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        Cl         H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  CH.sub.2 CH.sub.3                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub.3                                                                        H    O H  i-C.sub.3 H.sub.7                                                                  CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  H    CH.sub.3                                                                          CH.sub.3                                        CH.sub.3   H    S H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O CH.sub.3                                                                         H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3   H    O H  CH.sub.3                                                                           CH.sub.3 O                                                                        CH.sub.3                                        F          H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        Br         H    O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CH.sub.3 O H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR70## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                            H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CHCH.sub.2                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      n-C.sub.3 H.sub.7 SO.sub.2                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3 SO.sub.2                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3   H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR71## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 N(CH.sub.3)                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR72## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR73## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      n-C.sub.3 H.sub.7 SO.sub.2 O                                                             H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CF.sub.3 SO.sub.2 O                                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   3-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      NO.sub.2   5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3                                        CO.sub.2 CH.sub. 3                                                                       5-CF.sub.3                                                                         O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        6-Cl O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-Br O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-F  O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CO.sub.2 CH.sub.3                                                                        5-OCH.sub.3                                                                        O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CH.sub.3                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      i-C.sub.3 H.sub.7                                                                        H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      SO.sub.2 OCH.sub.2 CF.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      OCH.sub.2 CH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR74## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                      H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                       ##STR75## H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                          H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 OCH.sub.3                                                                       H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 OCH.sub.2 CH.sub.3                                                              H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      CH.sub.2 CO.sub.2 Et                                                                     H    O H  H    CH.sub.3 O                                                                        CH.sub.3 O                                      __________________________________________________________________________

                  TABLE 9                                                         ______________________________________                                         ##STR76##                                                                    R.sub.1       R.sub.2   R.sub.9   IR SO.sub.2 NCO                             ______________________________________                                        NO.sub.2      H         H         2230 cm.sup.-1                              Cl            H         H         2240 cm.sup.-1                              CO.sub.2 CH.sub.3                                                                           H         H         2230 cm.sup.-1                              CH.sub.3      H         H         2250 cm.sup.-1                              F             H         H                                                     Br            H         H                                                      ##STR77##    H         H                                                     CH.sub.3 SO.sub.2                                                                           H         H         2240 cm.sup.-1                              CH.sub.3 SO.sub.2                                                                           H         H                                                     CF.sub.3      H         H                                                     SO.sub.2 N(CH.sub.3).sub.2                                                                  H         H         2240 cm.sup.-1                               ##STR78##    H         H                                                     CH.sub.3 SO.sub.2 O                                                                         H         H         2240 cm.sup.-1                              CF.sub.3 SO.sub.2 O                                                                         H         H                                                     NO.sub.2      3-Cl      H                                                     NO.sub.2      5-Cl      H                                                     NO.sub.2      6-Cl      H                                                     NO.sub.2      5-Br      H                                                     NO.sub.2      5-CF.sub.3                                                                              H                                                     NO.sub.2      5-OCH.sub.3                                                                             H                                                     NO.sub.2      H         CH.sub.3  2240 cm.sup.-1                              CO.sub.2 CH.sub.3                                                                           H         CH.sub.3                                              CO.sub.2 CH.sub.3                                                                           H         CH.sub.2 CH.sub.3                                     CO.sub.2 CH.sub.3                                                                           H         i-C.sub.3 H.sub.7                                     Cl            H         CH.sub.3                                              CH.sub.3      H         CH.sub.3                                              CH.sub.2 CH.sub.3                                                                           H         H                                                     i-C.sub.3 H.sub.7                                                                           H         H                                                     SO.sub.2 OCH.sub.2 CF.sub.3                                                                 H         H                                                     OCH.sub.2 CH.sub.3                                                                          H         H                                                      ##STR79##    H         H                                                     CH.sub.2 SO.sub.2 N(CH.sub.3).sub.2                                                         H         H                                                      ##STR80##    H         H                                                     CH.sub.2 SO.sub.2 N(CH.sub.3)Et                                                             H         H                                                     CH.sub.2 OCH.sub.3                                                                          H         H                                                     CH.sub.2 OCH.sub.2 CH.sub.3                                                                 H         H                                                     CH.sub.2 CO.sub.2 CH.sub.3                                                                  H         H                                                     CH.sub.2 CO.sub.2 Et                                                                        H         H                                                     OCH.sub.3     H         H                                                     ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE 10                                                        ______________________________________                                                    Weight Percent*                                                               Active                                                                        Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, New Jersey, but other solids, either mined or manufactured,may be used. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid diluents andsolvents are described in Marsden, "Solvents Guide," 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as wellas Sisely and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc., New York, 1964, list surfactants and recommendeduses. All formulations can contain minor amounts of additives to reducefoaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, March 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 17

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-                                                         80%                                              (2-nitrophenyl)methanesulfonamide                                             sodium alkylnaphthalenesulfonate                                                                           2%                                               sodium ligninsulfonate       2%                                               synthetic amorphous silica   3%                                               kaolinite                    13%                                              ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 18

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-                                                   50%                                               (2-nitrophenyl)methanesulfonamide                                             sodium alkylnaphthalenesulfonate                                                                           2%                                               low viscosity methyl cellulose                                                                             2%                                               diatomaceous earth          46%                                               ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 19

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable Powder of Example 18                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 20

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-                                                     25%                                             (2-nitrophenyl)methanesulfonamide                                             anhydrous sodium sulfate      10%                                             crude calcium ligninsulfonate  5%                                             sodium alkylnaphthalenesulfonate                                                                             1%                                             calcium/magnesium bentonite   59%                                             ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 21

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                       25%                                              bonyl]-1-(2-nitrophenyl)methanesulfonamide                                    polyoxyethylene sorbitol hexaoleate                                                                         5%                                              highly aliphatic hydrocarbon oil                                                                           70%                                              ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 22

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-                                                          20%                                              (2-nitrophenyl)methanesulfonamide                                             sodium alkylnaphthalenesulfonate                                                                           4%                                               sodium ligninsulfonate       4%                                               low viscosity methyl cellulose                                                                             3%                                               attapulgite                  69%                                              ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 23

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]amino-                                                      1%                                               sulfonylmethyl]benzoic acid, methyl ester                                     N,N--dimethylformamide       9%                                               attapulgite granules         90%                                              (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 24

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-                                                        40%                                               (2-methylsulfonyloxyphenyl)methanesulfonamide                                 polyacrylic acid thickener 0.3%                                               dodecylphenol polyethylene glycol ether                                                                  0.5%                                               disodium phosphate           1%                                               monosodium phosphate       0.5%                                               polyvinyl alcohol          1.0%                                               water                      56.7%                                              ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 25

    ______________________________________                                        Solution                                                                      ______________________________________                                        2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocar-                                                          5%                                                 bonyl]aminosulfonylmethyl]benzoic acid,                                       methyl ester                                                                  water                     95%                                                 ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 26

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-                                                       0.1%                                             aminosulfonylmethyl]benzoic acid, methyl                                      ester                                                                         attapulgite granules        99.9%                                             (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 27

    ______________________________________                                        Granule                                                                       ______________________________________                                        N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl] -1-                                                        80%                                               (2-nitrophenyl)methanesulfonamide                                             wetting agent                1%                                               crude ligninsulfonate salt (containing                                                                    10%                                               5-20% of the natural sugars)                                                  attapulgite clay             9%                                               ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 28

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-                                                          99%                                             (2-nitrophenyl)methanesulfonamide                                             silica aerogel               0.5%                                             synthetic amorphous silica   0.5%                                             ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 29

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-                                                    90%                                              (2-nitrophenyl)methanesulfonamide                                             dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged. cl EXAMPLE 30

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                     40%                                               aminosulfonylmethyl]benzoic acid, methyl                                      ester                                                                         sodium ligninsulfonate      20%                                               montmorillonite clay        40%                                               ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 31

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]amino-                                                       35%                                              sulfonylmethyl]benzoic acid, methyl ester                                     blend of polyalcohol carboxylic                                                                             6%                                              esters and oil soluble petroleum                                              sulfonates                                                                    xylene                       59%                                              ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 32

    ______________________________________                                        Dust                                                                          ______________________________________                                        2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-                                                      10%                                               bonyl]aminosulfonylmethyl]benzoic acid,                                       methyl ester                                                                  attapulgite                 10%                                               Pyrophyllite                80%                                               ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

Utility

The compounds of the present invention are active herbicides. They haveutility for broad-spectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,parking lots, drive-in theaters, around billboards, highway and railroadstructures or under perimeter fences. Alternatively, the subjectcompounds are useful for the selective pre- or postemergence weedcontrol in crops, such as wheat, barley, corn, rice and soybeans.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as selective orgeneral herbicides, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.01 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for selective weed control orfor situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any otherherbicides, examples of which are those of the triazine, triazole,uracil, urea, amide, diphenylether, carbamate and bipyridylium types.Especially useful are combinations of the compounds of this inventionwith S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate;2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide;S-ethyl-N,N-hexamethylenethiolcarbamate;1-α,α-dimethylbenzyl-3-p-tolylurea;1-(α,α-dimethylbenzyl)-3-methyl-3-phenylurea;2,4-dichlorophenyl-3-methoxy-4-nitrophenyl ether;2,4,6-trichlorophenyl-4'-nitrophenyl ether;4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate;O-ethyl-O-(3-methyl-6-nitrophenol)-N-sec-butyl phosphoramid-thioate;S-(1-methyl-1-phenethyl)piperidine-1-carbathioate;2-chloro-2',6'-diethyl-N-(N-propoxyethyl)acetanilide;4-ethoxymethoxybenz-2',3'-dichloranilide;2-benzthiazol-2-iloxy-N-methylacetoanilide;5-t-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one;3',4'-dichloropropionanilide; andN-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine.

The herbicidal properties of the subject compounds were discovered in anumber of greenhouse tests. The test procedures and results follow.

Test A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated preemergence with the chemicals dissolved in anon-phytotoxic solvent. At the same time, cotton having five leaves(including cotyledonary ones), bush beans with the third trifoliate leafexpanding, crabgrass, barnyardgrass and wild oats with two leaves,cassia with three leaves (including cotyledonary ones), morningglory andcocklebur with four leaves (including the cotyledonary ones), sorghumand corn with four leaves, soybean with two cotyledonary leaves, ricewith three leaves, wheat with one leaf, and nutsedge with three to fiveleaves were sprayed. Treated plants and controls were maintained in agreenhouse for sixteen days, whereupon all species were compared tocontrols and visually rated for response to treatment. The ratings arebased on a numerical scale extending from 0=no injury, to 10=completekill. The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

S=albinism;

U=unusual pigmentation; and

6Y=abscised buds or flowers.

The ratings for the compounds tested by this procedure are presented inTable A. It will be seen that certain of the compounds tested haveutility for selective weed control in corn, rice and wheat.

    ______________________________________                                        Table Structures                                                              ______________________________________                                         ##STR81##                Compound 1                                           ##STR82##                Compound 2                                           ##STR83##                Compound 3                                           ##STR84##                Compound 4                                           ##STR85##                Compound 5                                           ##STR86##                Compound 6                                           ##STR87##                Compound 7                                           ##STR88##                Compound 8                                           ##STR89##                Compound 9                                           ##STR90##                Compound 10                                          ##STR91##                Compound 11                                          ##STR92##                Compound 12                                          ##STR93##                Compound 13                                          ##STR94##                Compound 14                                          ##STR95##                Compound 15                                          ##STR96##                Compound 16                                          ##STR97##                Compound 17                                          ##STR98##                Compound 18                                          ##STR99##                Compound 19                                          ##STR100##               Compound 20                                          ##STR101##               Compound 21                                          ##STR102##               Compound 22                                          ##STR103##               Compound 23                                          ##STR104##               Compound 24                                          ##STR105##               Compound 25                                          ##STR106##               Compound 26                                          ##STR107##               Compound 27                                          ##STR108##               Compound 28                                          ##STR109##               Compound 29                                          ##STR110##               Compound 30                                          ##STR111##               Compound 31                                          ##STR112##               Compound 32                                          ##STR113##               Compound 33                                          ##STR114##               Compound 34                                          ##STR115##               Compound 35                                          ##STR116##                                                                   ______________________________________                                                                  Compound 36                                     

    TABLE A       Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Cmpd. 5 Cmpd. 6 Cmpd. 7 Cmpd. 8 Cmpd.     9 Cmpd. 10 Cmpd. 11 Cmpd. 12 Rate kg/ha 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4     0.4 0.4 0.4 0.4       POST-EMERGENCE Bush bean 7C,9G,6Y 5C,9G,6Y 5C,9G,6Y 9D,9G,6Y 3C,9G,6Y     9C 9C 6C,9G 9C 9D,9G,6Y 4C,9G,6Y 3C,3G,6Y Cotton 6C,9G 6C,9G 3C,3H,8G     6C,9G 2C,2H,7G 6C,9G 6C,9G7C,9G 9C 5C,9G 6C,9G 3C,2H,5G Morningglory 10C     5C,9G 9C 10C 2C,9H 10C 10C 5C,9G 10C 10C 5C,9G 3C,7G Cocklebur 3C,9G 4G     9C 9C 3C,9G 2C,8G 9C 9C 10C 3C,9H 4C,9G 1C,4G Cassia 1C,9G 1C,2H 3C,7G     2C,4G 1C 6C,9G 6C,9G 5C,9G 9C 3C,4H 5C 1C Nutsedge 4C,9G 1C,7G 9G 2C,8G     0 9C 6C,9G 1C,8G 2C,9H 7G 1C,6G 4G Crabgrass 2G 2C,7G 1H 2C,8G 0 4C,8G     5C,9G 4G 9C 1C,3H 1C,5G 1C Barnyardgrass 3G 2C,5H 2C,8H 3C,9H 0 2C,6G     5C,9H 2C,9H 9C 3C,8H 9H 0 Wild Oats 0 3G 0 2C,3G 0 2G 1C,9G 1C,6G 2C,7G     2G 0 0 Wheat 0 2G 0 2C,3G 0 4G 1C,9G 4G 2C,9G 2G 0 0 Corn 0 9G 2C,9H     3C,9G 2C,5H 1C,8H 5C,9G 2C,9H 5U,9G 5C,9H 3C,9H 0 Soybean 2C,9G 2C,9G     3C,9G 3C,9G 1C,4H 5C,9G 9C 3C,9H 5C,9G 3C,9G 2C,7G 1C,2H Rice 1C 3C,9G     8G 2C,9G 2G 5G 5C,9G 1C,8G 5C,9G 2C,8G 2C,8G 0 Sorghum 1C,5G 1C,9G 9G     10C 2C,8H 2C,8G 9C 9G 9C 3C,9H 2C,9G 0 PRE-EMERGENCE Morningglory 9G 9G     9C 9G 8H 9G 10C 9C 9C 1C,8G 8G 9G Cocklebur 9H 9H 9H 9H 9H 9H 9H 9H 9H     1H 4C,9G 2C,5H Cassia 6C,9G 3C,5H 8G 3C,8G 3H 8G 2C,9G 5C,8G 2C,9G 3C 3C     2C Nutsedge 10E 7G 10E 1C,9G 0 10E 10E 10E 9G 1C 3G 2C,8G Crabgrass 2C     2C 1H 2C,5G 2G 2C,6G 5C,9G 2C,8G 5C,9G 1C,5G 2C 2C Barnyardgrass 3C     2C,6H 3C,9G 3C,9H 0 2C,9H 9H 4C,9G 9C,9H 2C,6H 3C,9H 2C Wild Oats 0     2C,5G 2C,6G 1C,5G 0 5G 1C,8G 2C,8G 4C,9G 5G 4G 0 Wheat 0 9G 7G 2C,9H 0     5G 9G 7G 2C,9G 6G 6G 0 Corn 2C,9H 9G 2C,9H 10H 1C,3G 9G 5C,9G 9G 10H     2C,8G 2C,8G 2C Soybean 9G,2H,7X 2C,6H 2C,7H 9H 1C 9H 9H 8H 9H 1C 2C,6G     1H Rice 3C,8G 10E 3C,9H 10E 2C,6G 2C,8G 10E 5C,9H 10E 4C,8H 3C,8G 4G     Sorghum 7H 5C,9H 9H 8C,9H 1C,3G 9G 6C,9G 2C,9C 5C,9H 3C,9G 2C,9G     5G          Cmpd. 13 Cmpd. 14 Cmpd. 15 Cmpd. 16 Cmpd. 17 Cmpd. 18 Cmpd.     19 Cmpd. 20 Cmpd. 21 Cmpd. 22 Cmpd. 23 Cmpd. 24 Rate kg/ha 0.4 0.4 0.4     0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4       POST-EMERGENCE Bush bean 5C,8G,6Y 4S,8G,6Y 5S,9G,6Y 0 0 9C 5C,9G 6C,9G     9C 3C,9G,6Y 4S,8G,6Y 1C Cotton 5C,9G 3C,3H,5G 5C,9G 0 1C,3H 9C 6C,9G     6C,9G 6C,9G 6C,9G 2C,2H 0 Morningglory 4C,9G 3C,8G 3C,8G 0 0 10C 5C,9G     4C,9G 4C,9G 2C,7G 2C,5H 0 Cocklebur 3G 3C,8H 3C,9G 0 0 3C,9G 4G 6C,9G 9C     3C,9G 3C 0 Cassia 3C 2C 3C 0 0 3C,7G 2C,3G 3C,3H 4C,3H 3C 2C 0 Nutsedge     1C 3C,9G 0 0 0 9C 9G 2C,8G 2C,8G 1C,9G 3C,8G 0 Crabgrass 2G 0 1C,3G 0 0     9C 5C,8G 3C,8G 6C,9G 1C,4G 3C,8G 0 Barnyardgrass 3G 0 3C,9H 0 0 6C,9H3C,9     H 2C,9H 5C,9H 3C,8H 4C,9H 0 Wild Oats 0 0 0 0 0 7G 3C,8G 2C,8G 9G 4G     1C,9G 0 Wheat 0 0 3G 0 0 2C,8G 4C,8G 4C,7G 3C,9G 4G 2C,9G 0 Corn 1C,4G     1C,3H 2C,7H 0 0 3U,9G 8U,9C 2U,9G 8U,9G2C,8G 2C,8G 0 Soybean 2C,4H     1C,3H1C,3H 0 1C,6G 6C,9G 4C,9G 9C 5C,9G 2C,9G 2C,2H 0 Rice 1C,6G 3G     1C,6G 0 0 2C,6G 5C,9G 4C,8G 4C,9G 2C,7G 4C,7G 0 Sorghum 2C,8H 1C,3G     2C,9H 0 0 2C,9G 9C 3C,9G 9C 2C,9G 3C,9G 0 PRE-EMERGENCE Morningglory 9G     8G 9G 0 1C,5H 9G 5C,9G 9C 9G 3C,6G 2C 6G Cocklebur 9G 8H 8H 0 3G 9H 9H     9H 9H 9H 3H 2H Cassia 2C 5G 2C 0 2C 9G 4C,7G 2C,8G 4C,9G 3C 2C 1C     Nutsedge 3G 4G 5G 0 0 10E 10E 10E 10E 10E 1C 0 Crabgrass 1C 0 1C,3G 0 0     2C,9G 9G,4C 4C,9G 5C,9G 4G 3G 0 Barnyardgrass 1C,3G 4G 8H,2C 0 1C 9H 9H     9H 9H 3C,8G 4C,8G 2C Wild Oats 2G 2G 5G 0 0 1C,8G 4C,9H 3C,9H 4C,9H     2C,8G 8G 0 Wheat 7G 2G 8G 0 0 9G 9H 9H 3C,9H 2C,8G 1C,8G 0 Corn 2C,8G     1C,6G 9G 0 0 9G 9H 9H 10E 3C,8H 4C,8H 2C,4G Soybean 1C 1C 2C 0 0 9H 9H     9H 9H 1C,2H 3G 0 Rice 5C,8H 1C,6G 5C,9H 0 0 10E 10E 10E 10E 9H 2C,8H 1C     Sorghum 3C,8H 2C,7H 3C,9H 0 0 5C,9H 5C,9G 6C,9G 6C,9H 2C,9G 2C,9G     1C,5G     Cmpd. 25 Cmpd. 26 Cmpd. 27 Cmpd. 28 Cmpd. 29 Cmpd. 30 Cmpd. 31     Cmpd. 32 Cmpd. 33 Cmpd. 34 Cmpd. 35 Cmpd. 36 Rate kg/ha 0.4 0.4 0.4 0.4     0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4       POST-EMERGENCE Bush bean 1C 0 2C,6F 1C 2C,5G 9C 5C,9G,6Y 1C 0 0 0 0     Cotton 2C,2H 2C,4G 2C,2H 1C 1C,2G 9C 5C,8G 0 1C 0 0 0 Morningglory 2C,7H     2C,2H 4C,9G 1C 2C 10C 4C,8H 1C 0 0 00 Cocklebur 0 0 3C,7G 1C 1C,5G 9C     4C,9G 0 1C,6H 0 0 0 Cassia 2C 0 3C 0 5G 9C 4C,6H 0 0 0 0 0 Nutsedge 0 0     2G 0 1C 9C 0 0 0 0 0 0 Crabgrass 1C,7G 0 2C,5G 0 0 9C 9C 2G 0 0 0 0     Barnyardgrass 1C,5H 0 3C,8H 0 0 9C 9C 0 0 0 0 0 Wild Oats 0 0 0 0 0     2C,9G 0 2G 0 0 0 0 Wheat 0 0 8G 0 0 3C,9G 5U,9G 0 0 0 0 0 Corn 1C,6H 0     2C,7H 0 0 5U,9C 7U,9C 1C 0 0 0 0 Soybean 2C 0 1C,1H 1C 1C 5C,9G 5C,9G 3H     0 0 0 0 Rice 1C,5G 0 2C,7G 0 0 3C,9G 5C, 9G 2G 0 0 0 0 Sorghum 2C,9G 0     9G 0 0 5U,9C 10C 2C,5G 0 0 0 0 PRE-EMERGENCE Morningglory 9G 2C,9G 9G     1C,3H 2C 9C 2C,4H 0 0 0 0 0 Cocklebur 5H 2C 7H 0 2G 9H 2C,6H 0 0 0 0 0     Cassia 2C 2C 2C 2C 2C 5C,9G 3C 0 0 0 0 0 Nutsedge 1C 0 0 1C,8G 4G 10E     2C,5G 0 0 0 0 0 Crabgrass 3G 2G 1C,5G 2G 2G 2C,9G 3C,6G 0 0 0 0 0     Barnyardgeass 2C,5G 4G 2C,8H 1C 1C,2H 2C,9H 9H 0 0 0 0 0 Wild Oats 2C 1C     1C 0 3G 2C,9G 2C,4G 0 0 0 0 0 Wheat 1C,7G 2G 1C,9G 0 2G 2C,9G 5C,9H 0 0     0 0 0 Corn 2C,8G 2C,7G 2C,9G 1C 1C,3G 3C,9G 10H 1C,3H 0 0 0 0 Soybean 0     0 1C,2G 1C,1H 2G 9H 2C,6H 0 0 0 0 0 Rice 2G 0 3G 0 1C 10E 9H 1C 0 0 0 0     Sorghum 1C,9G 2C,4G 5C,9H 1C 1C,7G 2C,9H 6C,9H 2C,4H 0 0 0 0     It is noted that certain compounds tested showed no activity at the level     tested but it is thought they would have activity at higher levels.

It is noted that certain compounds tested showed no activity at thelevels tested but it is thought they would have activity at higherlevels.

Test B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pensylvanicum), pigweed (Amaranthus retroflexus), morningglory(Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa),velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A12.5 cm diameter plastic pot was also filled with prepared soil andplanted with rice and wheat. Another 12.5 cm pot was planted withsugarbeets. The above four containers were treated pre-emergence withseveral test compounds within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B.

It should be noted that some of the compounds tested are useful as pre-or post-emergence treatment for weed control in crops such as wheat.

                  TABLE B                                                         ______________________________________                                        PRE-EMERGENCE ON                                                              FALLSINGTON SILT LOAM                                                         ______________________________________                                                   Compound 1  Compound 2                                             Rate kg/ha   .060     .250     .060   .250                                    ______________________________________                                        Crabgrass    0        0        0      0                                       Barnyardgrass                                                                              0        0        0      0                                       Sorghum      2G       4G       6G,3H  8G,5H                                   Wild Oats    0        0        0      0                                       Johnsongrass 0        5E       5G,3H  5G,5H                                   Dallisgrass  0        0        0      0                                       Giant foxtail                                                                              0        0        0      0                                       Ky. bluegrass                                                                              0        3G       0      3G                                      Cheatgrass   0        0        0      3G                                      Sugarbeets   3G       7G,5H    0      5G,3H                                   Corn         0        0        0      0                                       Mustard      8G,5C    9G,8C    4G     5G,5H                                   Cocklebur    0        0        0      0                                       Pigweed      6G       9G,9C    3G     10C                                     Nutsedge     0        0        0      0                                       Cotton       0        0        0      2G                                      Morningglory 0        0        0      3G                                      Cassia       0        0        0      0                                       Teaweed      0        0        0      0                                       Velvetleaf   0        3G,3H    0      0                                       Jimsonweed   0        0        0      0                                       Soybean      0        0        0      2G                                      Rice         0        0        4G     6G,3H                                   Wheat        0        0        0      0                                       ______________________________________                                                   Compound 3  Compound 4                                             Rate kg/ha   .060     .250     .060   .250                                    ______________________________________                                        Crabgrass    0        3G       0      0                                       Barnyardgrass                                                                              0        3G       2G     4G                                      Sorghum      0        4G,2H    7G,5H  9G,9C                                   Wild Oats    0        0        0      3G                                      Johnsongrass 0        4G       7G,5H  8G,5H                                   Dallisgrass  0        0        0      0                                       Giant foxtail                                                                              0        3G       0      5G,3H                                   Ky. bluegrass                                                                              0        4G       0      0                                       Cheatgrass   0        0        0      5G                                      Sugarbeets   3G       8G,8C    6G     8G,8C                                   Corn         0        0        0      5G,3H                                   Mustard      7G,5H    9G,8C    5G,3H  7G,5H                                   Cocklebur    0        0        0      0                                       Pigweed      3G       9G,9C    0      9G,8C                                   Nutsedge     0        0        0      0                                       Cotton       0        0        0      4G,3H                                   Morningglory 0        3H       0      5G,5H                                   Cassia       0        3G       0      3G                                      Teaweed      0        6G,3C    0      0                                       Velvetleaf   0        3G,3H    0      2C                                      Jimsonweed   0        0        0      2G                                      Soybean      0        2G       0      4G,2H                                   Rice         3G       5G       3G     7G,3H                                   Wheat        0        0        0      3G                                      ______________________________________                                                   Compound 6  Compound 7                                             Rate kg/ha   .060     .250     .060   .250                                    ______________________________________                                        Crabgrass    0        0        0      6G                                      Barnyardgrass                                                                              0        4G       4G     8G,5H                                   Sorghum      3G       6G,3H    9G,9C  10C                                     Wild Oats    0        0        3G     2G                                      Johnsongrass 0        3H       7G,5H  8G,5H                                   Dallisgrass  0        0        2G     3G                                      Giant foxtail                                                                              0        0        5G,2C  8G,5H                                   Ky. bluegrass                                                                              0        3G       5G     6G                                      Cheatgrass   0        0        5G     5G,2C                                   Sugarbeets   4G       6G       7G,5H  8G,8C                                   Corn         0        0        3G     2C                                      Mustard      9G,9C    10C      7G,3H  8G,8C                                   Cocklebur    0        0        0      0                                       Pigweed      10E      10E      0      5G                                      Nutsedge     0        9G       0      5G                                      Cotton       0        4G       0      5G,5H                                   Morningglory 0        3G       4G,5H  8G,5C                                   Cassia       0        3G       0      8G,3C                                   Teaweed      0        5G       3G     5G,2C                                   Velvetleaf   5G,3H    7G,5H    2G     5G,3H                                   Jimsonweed   0        5G,5C    0      5G,3C                                   Soybean      3G       5G,2H    3G     7G,3C                                   Rice         3G       5G       5G     7G,3C                                   Wheat        0        3G       3G     3G                                      ______________________________________                                                   Compound 8  Compound 9                                             Rate kg/ha   .060     .250     .060   .250                                    ______________________________________                                        Crabgrass    0        0        3G     6G                                      Barnyardgrass                                                                              0        6G,2H    7G,3H  8G,7C                                   Sorghum      4G,3H    8G,5H    10C    10C                                     Wild Oats    0        3G       2G     4G                                      Johnsongrass 0        3H       7G,5H  8G,5H                                   Dallisgrass  0        3G       3G     6G                                      Giant foxtail                                                                              0        3G       8G,5H  9G,9C                                   Ky. bluegrass                                                                              0        3G       6G     7G,3C                                   Cheatgrass   0        3G       8G,8C  8G,9C                                   Sugarbeets   6G       7G,5C    8G,8C  9G,9C                                   Corn         0        4G,3H    6G,5H  8G,5H                                   Mustard      8G,8C    9G,9C    10C    10C                                     Cocklebur    0        3H       5G,4H  6G,5H                                   Pigweed      5G,5C    10E      8G     10E                                     Nutsedge     5G       8G       4G     7G                                      Cotton       2H       6G,5H    4G     8G,5H                                   Morningglory 0        3G,5H    7G,5H  9G,5C                                   Cassia       0        4G       8G,3C  9G,5C                                   Teaweed      5G,2C    6G,2C    5G,2C  6G,2C                                   Velvetleaf   3G,3H    8G,5H    3G,3H  6G,5H                                   Jimsonweed   5G,3C    5G,3C    7G,5C  8G,8C                                   Soybean      0        4G,2C    3G,2C  8G,5H                                   Rice         4G       5G       9G,9C  10E                                     Wheat        0        4G       4G     5G                                      ______________________________________                                                   Compound 18 Compound 19                                            Rate kg/ha   .030      .120    .030   .120                                    ______________________________________                                        Crabgrass    5G       6G       4G     6G,3C                                   Barnyardgrass                                                                              3G       4G       2G     4G                                      Sorghum      7G,3H    9G,3H    9G,5H  10C                                     Wild Oats    0        0        3G     6G                                      Johnsongrass 4G       6G,3H    7G,3H  8G,5H                                   Dallisgrass  0        0        0      2G                                      Giant foxtail                                                                              0        4G       3G     7G,5H                                   Ky. bluegrass                                                                              3G       5G       6G,3H  6G,5C                                   Cheatgrass   0        5G       8G     10E                                     Sugarbeets   4G,3H    6G,3H    4G,3H  6G,5H                                   Corn         0        3G,3H    0      6G,5H                                   Mustard      7G,7C    9G,9C    4G     7G,8C                                   Cocklebur    0        4G,3H    0      0                                       Pigweed      0        --       --     --                                      Nutsedge     7G       9G,5C    0      0                                       Cotton       3G       4G,3H    0      3G                                      Morningglory 0        0        0      4G,3H                                   Cassia       3G       4G       0      0                                       Teaweed      6G       6G       4G     3G                                      Velvetleaf   4G       5G,3H    0      3G                                      Jimsonweed   0        5G,5C    0      3G                                      Soybean      3G       5G       3G     2G,2C                                   Rice         0        5G,3H    7G,3H  10E                                     Wheat        0        2G       3G     5G                                      ______________________________________                                                   Compound 20 Compound 21                                            Rate kg/ha   .030     .120     .030   .120                                    ______________________________________                                        Crabgrass    4G       5G       5G     7G,3C                                   Barnyardgrass                                                                              3G       3G       2G     5G                                      Sorghum      4G,3H    6G,5H    9G,9C  10C                                     Wild Oats    0        3G       4G     6G                                      Johnsongrass 2G       5G,3H    5G     7G,3H                                   Dallisgrass  0        0        2G     3G                                      Giant foxtail                                                                              0        4G,3C    6G,3H  8G,5H                                   Ky. bluegrass                                                                              3G       5G       7G,7C  8G,8C                                   Cheatgrass   0        5G       8G     10E                                     Sugarbeets   3G       7G,5H    6G,5H  7G,7C                                   Corn         0        3G       3G     9G,9C                                   Mustard      8G,3C    8G,8C    6G,3H  8G,8C                                   Cocklebur    --       3G       3G     3G                                      Pigweed      --       --       --     --                                      Nutsedge     0        6G       0      5G                                      Cotton       0        0        0      3G                                      Morningglory 0        0        4G,3H  7G,5H                                   Cassia       0        0        0      2C                                      Teaweed      0        3G       --     3G                                      Velvetleaf   0        3G       0      2G                                      Jimsonweed   0        5G,3C    4G     7G,3C                                   Soybean      0        2G       0      3G                                      Rice         3G       4G       7G,3H  9G,9C                                   Wheat        0        0        4G     6G                                      ______________________________________                                    

Test C

Twenty-five cm diameter plastic pots filled with Fallsington silt loamwere planted with soybeans, cotton, alfalfa, corn, rice, wheat, sorghum,velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), Cassia(Cassia tora), morningglory (Ipomoea hederacea), jimsonweed (Daturastramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitariasp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloacrusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua).Approximately 21/2 weeks after planting, the young plants and the soilaround them were sprayed overall with the test chemicals dissolved in anon-phytotoxic solvent. Two weeks after treatment, all species werecompared to untreated controls and visually rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table C. Selected compounds tested by thisprocedure are useful for the post-emergence control of weeds in wheat,corn, rice and soybeans.

                                      TABLE C                                     __________________________________________________________________________    Over-the-Top Soil/Foliage Treatment                                           __________________________________________________________________________             Compound 1           Compound 2                                                                            Compound 3                                                                            Compound 4                      Rate kg/ha                                                                             0.063                                                                              0.250                                                                              0.250                                                                              1.0   0.250                                                                             0.063                                                                             0.063                                                                             0.063                                                                             0.031                                                                              0.063                                                                             0.125                                                                             0.250              __________________________________________________________________________    Soybeans 8G,5C                                                                              9G,9C                                                                              10G,7C                                                                             10G,3C                                                                              8G,5C                                                                             4G,3C                                                                             8G,4C                                                                             9G,1C                                                                             7G,5C                                                                              8G,7C                                                                             8G,7C                                                                             8G,6C              Velvetleaf                                                                             9G,5C                                                                              10G,6C                                                                             10C  9G,9C 2C  1C  8G,3C                                                                             7G,5C                                                                             4C   5G,1C                                                                             4G,5C                                                                             3C                 Sesbania 9G,4C                                                                              9G,6C                                                                              8G,4C                                                                              9G,7C 0   0   7G,5C                                                                             8G,4C                                                                             1C   0   3G,2C                                                                             5G,2C              Cassia   8G,4C                                                                              6G,6C                                                                              7G,3C                                                                              10G,1C                                                                              4G  0   7G,1C                                                                             7G  0    2G  3C  1G                 Cotton   6G   8G,3C                                                                              9G,4C                                                                              9G,6C 1C  0   3G  6G,2C                                                                             1C   1G,1C                                                                             6G,2C                                                                             1G,1C              Morningglory                                                                           9G,2C                                                                              9G,3C                                                                              9G,7C                                                                              8G,8C 6G,5C                                                                             6G,3C                                                                             8G,5C                                                                             7G,5C                                                                             7G,2C                                                                              7G,5C                                                                             8G,2C                                                                             8G,6C              Alfalfa  7G,2C                                                                              6G,2C                                                                              7G   9G,9C 1C  1C  1C  5G  2C   1G,2C                                                                             6G,3C                                                                             4G,5C              Jimsonweed                                                                             8G   5G   5G   4G,6C 0   0   1C  0   7G   0   7G  --                 Cocklebur                                                                              2G   8G   3G   8G,1C 0   0   8G,2C                                                                             7G,4C                                                                             3G,3C                                                                              1G,5C                                                                             8G  8G,8C              Sunflower                                                                              10G,2C                                                                             10G,5C                                                                             5G,2C                                                                              9G,5C 0   0   9G,7C                                                                             9G,3C                                                                             2C,1H                                                                              8G,7C                                                                             9G,5C                                                                             9G,7C              Mustard  10C  10C  9G,9C                                                                              10C   9G,9C                                                                             9G,6C                                                                             10C 9G  8G,8C                                                                              8G,8C                                                                             9G,5C                                                                             9G,9C              Sugarbeets                                                                             7G   8G   9G,5C                                                                              9G,5C 8G,5C                                                                             5G  8G  8G,4C                                                                             8G   8G,3C                                                                             8G  9G,7C              Corn     0    3G   0    2U    8G,1C                                                                             5G,2C                                                                             5G,2H                                                                             8G,2H                                                                             8G,5H                                                                              5G,1U                                                                             9G,7U                                                                             7G,3U              Crabgrass                                                                              0    0    0    0     1C  2C  0   3G  0    1C  0   1G,2C              Rice     0    0    0    0     6G,1C                                                                             5G,1C                                                                             0   0   4G   3G  6G,3C                                                                             5G,1C              Nutsedge 6G   8G   3G   7G    0   0   5G  6G  0    0   0   0                  Barnyardgrass                                                                          0    0    0    8G,2C 0   0   0   2G  2G   5G,3C                                                                             6G,3H                                                                             8G,3C              Wheat    0    0    0    0     0   0   0   4G  0    1G  4G  3G                 Giant foxtail                                                                          0    2G   0    0     0   0   0   6G,2C                                                                             0    2G  4G  5G,3C              Wild Oats                                                                              0    0    2G   0     0   0   0   0   0    0   0   0                  Sorghum  0    2G   0    0     7G  6G  8G,2H                                                                             2C  7G   7G,2U                                                                             10C 7G,6U              Johnsongrass                                                                           0    0    --   --    --  --  --  --  4G   --  8G  --                 Field Bindweed                                                                         3G   3G   --   --    --  --  --  --  --   --  0   --                 __________________________________________________________________________             Compound 6 Compound 7 Compound 8            Compound 9               Rate kg/ha                                                                             0.500                                                                              0.125 0.500                                                                              0.125 0.016                                                                              0.063 0.125                                                                              0.500 0.500                                                                              0.125               __________________________________________________________________________    Soybeans 10G,9C                                                                             10G,2C                                                                              10G,4C                                                                             10C   10G,5C                                                                             10G,3C                                                                              10G,6C                                                                             10G,7C                                                                              10G,5C                                                                             9G,8C               Velvetleaf                                                                             9G,9C                                                                              9G,5C 9G,8C                                                                              9G,8C 9G,3C                                                                              9G,5C 10C  8G,9C 8G,7C                                                                              7G,5C               Sesbania 10C  10C   10C  10C   9G,5C                                                                              10C   10C  10C   9G,9C                                                                              9G,8C               Cassia   10G,5C                                                                             10G,5C                                                                              10G,5C                                                                             10G,5C                                                                              4G   9G,4C 7G,4C                                                                              10G   9G,5C                                                                              9G,7C               Cotton   10G,8C                                                                             9G,4C 9G,9C                                                                              9G,8C 4G,2C                                                                              6G    8G,4C                                                                              9G,4C 10G,9C                                                                             9G,9C               Morningglory                                                                           10C  10C   9G,8C                                                                              9G,8C 8G,3C                                                                              9G,9C 10G,2C                                                                             10G,2C                                                                              9G,9C                                                                              10G,7C              Alfalfa  7G,6C                                                                              7G    10G  8G    2G   0     7G   7G,3C 7G,4C                                                                              6G,4C               Jimsonweed                                                                             0    2G,2C --   --    8G   9G    5G   --    6C   4C                  Cocklebur                                                                              10G,9C                                                                             9G,1C 8G,4C                                                                              1G    8G,3C                                                                              9G,4C --   10G   10C  10G,7C              Sunflower                                                                              9G,8C                                                                              7G    10G,5C                                                                             8G    6G   8G    9G,2C                                                                              9G,7C 10C  10C                 Mustard  10C  10C   10G  9G,5C 10C  10C   9G,8C                                                                              9G,7C 10C  10C                 Sugarbeets                                                                             10C  8G,7C 9G,8C                                                                              9G,2C 3G   5G    8G   9G,2C 8G,7C                                                                              8G,7C               Corn     6G,2H                                                                              5G    10C  9G,2U 3G,3H                                                                              8G,3H 9G,2C                                                                              9G,1C 10C  10C                 Crabgrass                                                                              0    6G    9G,5C                                                                              9G    0    3G    3G   5G    8G,3C                                                                              8G,3C               Rice     4G   4G    5G,5C                                                                              8G,2C 1G   0     0    5G    9G,6C                                                                              9G,4C               Nutsedge 8G   8G    9G   3G    6G   6G,2C 6G   8G    7G,4C                                                                              3G                  Barnyardgrass                                                                          3G,2C                                                                              3G,2C 8G,6C                                                                              8G,4C 0    4G,4H 7G,5C                                                                              7G,5C 8G,7C                                                                              7G,5C               Wheat    0    0     5G,5C                                                                              5G    0    0     3G   6G    7G,3C                                                                              7G                  Giant foxtail                                                                          0    0     9G   9G    0    2G    5G   3G    9G,5C                                                                              8G,3C               Wild Oats                                                                              0    0     7G,5C                                                                              8G    0    0     2G   3G    6G   5G                  Sorghum  5G   3G    10G,5U                                                                             9G,5C 2H   7G    5G   7G,1C 9G,7U                                                                              9G,4U               Johnsongrass                                                                           --   --    --   --    --   --    --   --    --   --                  Field Bindweed                                                                         --   --    --   --    --   --    --   --    --   --                  __________________________________________________________________________            Compound 10  Compound 11                                                                            Compound 18                                                                           Compound 19                                                                           Compound 20                                                                           Compound 21             Rate kg/ha                                                                            0.500                                                                             0.125                                                                              0.031                                                                             0.500                                                                              0.125                                                                             0.125                                                                             0.031                                                                             0.125                                                                             0.031                                                                             0.125                                                                             0.031                                                                             0.125                                                                              0.031              __________________________________________________________________________    Soybeans                                                                              9G,6C                                                                             2G,1C                                                                              2G,1C                                                                             8G,5C                                                                              5G,5C                                                                             10C 10C 9G,7C                                                                             7G,6C                                                                             9G,8C                                                                             9G,7C                                                                             10G,3C                                                                             9G,8C              Velvetleaf                                                                            7G,5C                                                                             9G,7C                                                                              4G,4C                                                                             4G,3C                                                                              0   10C 10C 6G  6G,2C                                                                             9G,4C                                                                             6G  9G,5C                                                                              5G,4C              Sesbania                                                                              8G,4C                                                                             7G   5G  2C   0   10C 10C 0   0   9G,9C                                                                             7G,7C                                                                             8G   4G                 Cassia  3G,2C                                                                             0    0   5G,4C                                                                              2C  10C 9G,9C                                                                             3G,3C                                                                             1G,1C                                                                             9G,8C                                                                             5G,6C                                                                             9G,4C                                                                              8G                 Cotton  8G,5C                                                                             9G,7C                                                                              5G,3C                                                                             2G,3C                                                                              1C  10C 10C 9G  3G  9G,7C                                                                             9G,3C                                                                             9G,5C                                                                              8G,3C              Morningglory                                                                          9G,5C                                                                             8G,3C                                                                              8G,3C                                                                             7G   4G  10C 10C 2C  0   9G,7C                                                                             8G,2C                                                                             9G,3C                                                                              7G                 Alfalfa 2G,4C                                                                             3G   3G  5G   1G  10C 10C 2G,2C                                                                             2C  9G,7C                                                                             6G,3C                                                                             10C  8G,3C              Jimsonweed                                                                            --  --   0   0    0   9G,7C                                                                             9G,4C                                                                             9G  --  --  6G,2C                                                                             9G,7C                                                                              8G,2C              Cocklebur                                                                             7G,2C                                                                             10G,3C                                                                             2G  10G,4C                                                                             --  9G,9C                                                                             9G,7C                                                                             8G  0   9G,9C                                                                             6G  9G,5C                                                                              9G,2C              Sunflower                                                                             8G,3C                                                                             8G,2C                                                                              5G,2C                                                                             6G,5C                                                                              0   10C 10C 5G  0   10C 8G,5C                                                                             8G,7C                                                                              6G                 Mustard 9G,9C                                                                             9G,9C                                                                              8G,5C                                                                             9G,5C                                                                              0   10C 10C 9G  7G  10C 9G,9C                                                                             10C  10C                Sugarbeets                                                                            8G,4C                                                                             9G,7C                                                                              8G,5C                                                                             8G,7C                                                                              3G  10C 10C 6G,6C                                                                             2G,3C                                                                             9G  8G  9G,7C                                                                              6G                 Corn    7G,1H                                                                             7G,1C                                                                              7G,1C                                                                             9G   9G  9G,9C                                                                             9G,9C                                                                             9G,3C                                                                             8G  9G,7C                                                                             7G,3H                                                                             9G,9C                                                                              10C                Crabgrass                                                                             1G  8G,3C                                                                              7G,2C                                                                             3G   4G  8G,5C                                                                             7G  --  5G  7G  0   8G,4C                                                                              4G,3C              Rice    5G  8G,1C                                                                              8G,1C                                                                             2G   4G,2C                                                                             8G,4C                                                                             5G,2C                                                                             8G,7C                                                                             8G,7C                                                                             6G,4C                                                                             5G  10C  10C                Nutsedge                                                                              4G  9G,2C                                                                              8G,4C                                                                             0    0   10C 10C 0   0   9C  8G  10C  9G                 Barnyardgrass                                                                         7G,4C                                                                             7G,4C                                                                              8G,5C                                                                             7G   8G,4C                                                                             9G,5C                                                                             8G  0   0   9G,4C                                                                             6G  9G,8C                                                                              2G                 Wheat   5G  6G,2C                                                                              6G,2C                                                                             0    0   9G,3C                                                                             9G,2C                                                                             8G  8G  8G,2C                                                                             5G  9G,8C                                                                              8G,4C              Giant foxtail                                                                         7G  8G,1C                                                                              8G,3C                                                                             5G   5G  9G,5C                                                                             8G  9G,9C                                                                             9G,9C                                                                             8G,2C                                                                             5G  9G,5U                                                                              9G,2C              Wild Oats                                                                             2G  1G   3G  0    0   9G,3C                                                                             8G  8G,2C                                                                             7G  8G,4C                                                                             5G,1C                                                                             7G   0                  Sorghum 8G,1C                                                                             8G,1C                                                                              9G,1U                                                                             8G,1U                                                                              6G,2U                                                                             9C,7C                                                                             9G,7C                                                                             6G,6C                                                                             6G,4C                                                                             9G,6C                                                                             8G  10C  8G,5C              Johnsongrass                                                                          --  --   --  --   --  9G,8U                                                                             9G,8U                                                                             9G,7C                                                                             9G,6C                                                                             8G,7U                                                                             7G,3U                                                                             --   --                 Field Bindweed                                                                        --  --   --  --   --  --  5G  4G,5C                                                                             4G,5C                                                                             5G  8G  --   --                 __________________________________________________________________________                                                    Compound                                                                              Compound 23                                                  Rate kg/ha                                                                             0.125                                                                             0.031                                                                             0.125                                                                             0.031             __________________________________________________________________________                                           Soybeans 7G,4C                                                                             6G,3C                                                                             5G  3G                                                       Velvetleaf                                                                             7G,4C                                                                             5G,2C                                                                             0   0                                                        Sesbania 7G,6C                                                                             4G  0   0                                                        Cassia   8G,6C                                                                             2G,2C                                                                             2C  0                                                        Cotton   7G,3C                                                                             2G  2G  0                                                        Morningglory                                                                           8G,2C                                                                             2G  0   2G                                                       Alfalfa  4G,3C                                                                             0   2C  2C                                                       Jimsonweed                                                                             4G  2G  2C  0                                                        Cocklebur                                                                              2G  2G  2G  0                                                        Sunflower                                                                              2G,3C                                                                             1G  0   0                                                        Mustard  10C 7G,5C                                                                             4G,4C                                                                             0                                                        Sugarbeets                                                                             2G  4G  4G  0                                                        Corn     3G,2H                                                                             0   3G  0                                                        Crabgrass                                                                              0   0   0   0                                                        Rice     3G  0   0   0                                                        Nutsedge 0   0   0   0                                                        Barnyardgrass                                                                          0   0   0   0                                                        Wheat    0   2G  0   0                                                        Giant foxtail                                                                          1G  0   3G  0                                                        Wild Oats                                                                              0   0   0   0                                                        Sorghum  6G  5G,5C                                                                             6G  4G                                                       Johnsongrass                                                                           2G  0   3G  0                                                        Field Bindweed                                                                         3G  0   --  --                __________________________________________________________________________

Test D

Two ten-inch in diameter plastic pans lined with polyethylene linerswere filled with prepared Fallsington silt loam soil. One pan wasplanted with seeds of wheat (Triticum aestivum), barley (Hordeumvulgare), wild oats (Avena fatua), downy brome (Bromus tectorum),cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides),annual bluegrass (Poa annua), green foxtail (Setaria viridis),quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) andripgut brome (Bromus rigidus). The other pan was planted with seeds ofRussian thistle (Salsola kali), tansy mustard (Descuraina pinnata),smartweed (Polygonum pensylvanicum), tumble mustard (Sisymbriumaltissium) kochia (Kochia scoparia), shepherd's purse (Capsellabursa-pastoris), Matricaria inodora, black nightshade (Solanum nigrum),yellow rocket (Barbarea vulgaris), wild mustard (Brassica kaber), andwild buskwheat (Polygonum convolvulus). The above two pans were heatedpre-emergence. At the same time two pans in which the above plantspecies were growing were treated post-emergence. Plant height at thetime of treatment ranged from 1-15 cm depending on plant species.

The compounds applied were diluted with a nonphytotoxic solvent andsprayed over-the-top of the pans. An untreated control and a solventalone control were included for comparison. All treatments weremaintained in the greenhouse for 20 days at which time the treatmentswere compared to the controls and the effects visually rated. Therecorded data are presented in Table D. One of the compounds has utilityfor pre- and or post-emergence weed control in wheat and barley.

                                      TABLE D                                     __________________________________________________________________________                               Compound 2                                                   Compound 1       Pre-  Post-                                                  Pre-Emergence                                                                         Post-Emergence                                                                         Emergence                                                                           Emergence                                    Rate kg/ha                                                                              1/2 1   1/2 1    1/8   1/8                                          __________________________________________________________________________    wheat     1C,1G                                                                             1C,2G                                                                             1C,1G                                                                             0    7G    4C,7G                                        barley    0   1G  2C  1C   8G    5C,6G                                        wild oats 1C,2G                                                                             1C,3G                                                                             1C  0    2C,6G 5C,6G                                        downy brome                                                                             5G  5G  0   0    10C   7C,9G                                        cheatgrass                                                                              1C,6G                                                                             2C,8G                                                                             0   0    10C   10C                                          blackgrass                                                                              4G  1C,5G                                                                             2G  0    6C,8G 5C,8G                                        annual bluegrass                                                                        1C,5G                                                                             4G  0   5G   7C,9G 6C,8G                                        green foxtail                                                                           4G  6G  2G  2C,5G                                                                              8C,9G 9C,9G                                        quackgrass                                                                              5G  6G  2G  4G   4C,8G 5C,9G                                        Italian ryegrass                                                                        1C,4G                                                                             1C,5G                                                                             1G  6G   5C,8G 4C,7G                                        ripgut brome                                                                            5G  2C,7G                                                                             3G  3G   6C,9G 10C                                          Russian thistle                                                                         0   0   1C,2G                                                                             7C,8G                                                                              5C,4G 10C                                          tansy mustard                                                                           10E 10E 10C 10C  10C   10C                                          smartweed --  --  --  --   --    --                                           tumble mustard                                                                          10C 10C 10C 10C  10C   10C                                          kochia    3C,8G                                                                             2C,8G                                                                             3C,7G                                                                             2C,8G                                                                              9C,9G 10C                                          shepherd's purse                                                                        10C 10C 10C 10C  10C   10C                                          Matricaria inodora                                                                      9G  9G  10C 10C  9G    10C                                          black nightshade                                                                        6G  8G  0   3G   3C,8G 10C                                          yellow rocket                                                                           9G  9G  10C 10C  8C,9G 10C                                          wild mustard                                                                            10C 10C 10C 10C  10C   10C                                          wild buckwheat                                                                          2C,8G                                                                             2C,9G                                                                             10C 10C  6C,7G 10C                                          __________________________________________________________________________

Test E

A series of simulated rice paddy tests were conducted in a greenhouse.Compounds selected from within the scope of the present invention wereformulated and applied directly to the paddy water three days aftertransplanting of rice. "Early" plant response ratings (less than oneweek after application) were taken in some of the tests; "late" plantresponse ratings (5 to 6 weeks after application) were taken in alltests.

                  TABLE E                                                         ______________________________________                                                              Barnyard- Water  Arrow-                                 Rate Rice      Rice   grass     Chestnut                                                                             head                                   ai/ha                                                                              Early     Late   late      late   late                                   ______________________________________                                        Compound 1                                                                     50  --        0      0         9G     1G,2H                                  200  --        0      0         3G     0                                      Compound 6                                                                     50  0         0      10C       10C    4G                                     200  0         0      9C        10C    5G,3H                                  Compound 8                                                                     25  0         0      6G,8E     5G     9G                                     100  0         0      9G,9E     10C    10G,5C                                 Compound 18                                                                    50  0         4G     8C        10C    6G                                     200  0         9G     10C       10C    10E                                    Compound 22                                                                    50  0         0      0         0      0                                      200  0         0      0         0      0                                      ______________________________________                                    

Several of the compounds tested provided excellent control of weeds inrice without damage to the rice.

What is claimed is:
 1. A compound of the formula: ##STR117## wherein R₁is F, Cl, Br, CF₃, C₁ -C₃ alkoxy, C₁ -C₃ alkyl, NO₂, CO₂ R₄, SO₂ R₅, SO₂NR₆ R₇, SO₂ N(OCH₃)CH₃, SO₂ OCH₂ CF₃, OSO₂ R₅ or CH₂ L;L is SO₂ NR₆ R₇,OCH₃, OC₂ H₅, CO₂ CH₃ or CO₂ C₂ H₅ ; R₂ is H, Cl, Br, F, CF₃ or OCH₃ ;R₄ is C₁ -C₃ alkyl, CH₂ CH═CH₂, CH₂ CH₂ Cl, or CH₂ CH₂ OCH₃ ; R₅ is C₁-C₃ alkyl or CF₃ ; R₆ and R₇ are independently C₁ -C₃ alkyl; R₈ is H orCH₃ ; R₉ is H or C₁ -C₃ alkyl; R₃ is ##STR118## W is O or S; X is CH₃,OCH₃ or Cl; Y is CH₃, C₂ H₅, OCH₃, OC₂ H₅, CH₂ OCH₃, NH₂, NHCH₃ orN(CH₃)₂ ; Z is CH or N; X₁ is H, Cl, CH₃, OCH₃ or OC₂ H₅ ; X₂ is CH₃, C₂H₅, OCH₃ or OC₂ H₅ ; X₃ is CH₃ or OCH₃ ; and Y₁ is CH₃ or OCH₃ ; andtheir agriculturally suitable salts; provided that: (1) when W is S,then R₈ is H; (2) the total number of carbon atoms of R₆ and R₇ is lessthan or equal to 4; and (3) when X is Cl, then Z is CH and Y is NH₂,NHCH₃, N(CH₃)₂ or OCH₃.
 2. Compounds of claim 1 whereinR₂ is H; R₈ is H;and W is O.
 3. Compounds of claim 2 whereinR₁ is CF₃, NO₂, C₁ -C₃alkoxy, CO₂ R₄, SO₂ R₅, SO₂ NR₆ R₇, SO₂ N(OCH₃)CH₃ or OSO₂ R₅ ; R₉ is H;X₃ is OCH₃ ; and Y₁ is OCH₃.
 4. Compounds of claim 3 whereinR₄ is CH₃ orC₂ H₅ ; R₅ is CH₃ or CF₃ ; and R₆ and R₇ are independently CH₃ or C₂ H₅.5. Compounds of claim 4 wherein ##STR119##
 6. Compounds of claim 5whereinR₁ is CF₃, NO₂, CO₂ CH₃, SO₂ CH₃, SO₂ N(CH₃)₂, SO₂ N(OCH₃)CH₃ orOSO₂ CH₃.
 7. Compounds of claim 6 whereinX and Y are independently CH₃or OCH₃.
 8. The compound of claim 1,N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide.9. The compound of claim 1,N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide.10. The compound of claim 1,N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide.11. The compound of claim 1,N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide.12. The compound of claim 1,N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide.13. The compound of claim 1,2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 14. The compound of claim 1,2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 15. The compound of claim 1,2-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 16. The compound of claim 1,2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 17. The compound of claim 1,2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 18. The compound of claim 1,2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.
 19. The compound of claim 1,N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide.20. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 1and at least one of the following: surfactant, solid or liquid diluent.21. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 2and at least one of the following: surfactant, solid or liquid diluent.22. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 3and at least one of the following: surfactant, solid or liquid diluent.23. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 4and at least one of the following: surfactant, solid or liquid diluent.24. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 5and at least one of the following: surfactant, solid or liquid diluent.25. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 6and at least one of the following: surfactant, solid or liquid diluent.26. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 7and at least one of the following: surfactant, solid or liquid diluent.27. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of the compound of claim13 and at least one of the following: surfactant, solid or liquiddiluent.
 28. A method for controlling the growth of undesired vegetationwhich comprises applying to the locus to be protected an effectiveamount of a compound of claim
 1. 29. A method for controlling the growthof undesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 30. A method ofcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 31. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 4. 32. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 5. 33. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim6.
 34. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 7. 35. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of the compound of claim
 8. 36. A methodfor controlling the growth of undesired vegetation in rice whichcomprises applying to the locus to be protected an effective amount of acompound selected from: ##STR120## where R₁ is Cl, NO₂, CO₂ CH₃, SO₂CH₃, OSO₂ CH₃ or SO₂ N(CH₃)₂.
 37. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an herbicidally effective amount of a compound of claim 1 andan herbicidally effective amount of one or more compounds selected fromthe following:S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate;2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide;S-ethyl-N,N-hexamethylene-thiolcarbamate;1-α,α-dimethylbenzyl-3-p-tolylurea;1-(α,α-dimethylbenzyl)-3-methyl-3-phenylurea;2,4-dichlorophenyl-3-methoxy-4-nitrophenyl ether;2,4,6-trichlorophenyl-4'-nitrophenyl ether;4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate;O-ethyl-O-(3-methyl-6-nitrophenol)-N-sec-butyl phosphoramid-thioate;S-(1-methyl-1-phenethyl)piperidine-1-carbathioate;2-chloro-2',6'-diethyl-N-(N-propoxy-ethyl)acetanilide;4-ethoxymethoxybenz-2',3'-dichloroanilide;2-benzthiazol-2-iloxy-N-methylacetoanilide;5-t-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one;3',4'-dichloropropionanilide; andN-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine.
 38. A method according toclaim 37 where the compound of claim 1 is2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoicacid, methyl ester.